PEER-REVIEWED REVIEW ARTICLE bioresources.com Zambrano et al. (2020). “Nanocellulose & grammage,” BioResources 15(2), Pg#s to be added. 1 Using Micro- and Nanofibrillated Cellulose as a Means to Reduce Weight of Paper Products: A Review Franklin Zambrano, a Heather Starkey, a Yuhan Wang, a Camilla Abbati de Assis, a Richard Venditti, a Lokendra Pal, a Hasan Jameel, a Martin A. Hubbe, a Orlando J. Rojas, b and Ronalds Gonzalez a, * Based on publications related to the use of micro- and nanofibrillated cellulose (MNFC) in papermaking applications, three sets of parameters (intrinsic and extrinsic variables, furnish composition, and degree of dispersion) were proposed. This holistic approach intends to facilitate understanding and manipulation of the main factors describing the colloidal behavior in systems comprising of MNFC, pulp fibers, and additives, which directly impact paper product performance. A preliminary techno-economic assessment showed that cost reductions driven by the addition of MNFC in paper furnishes could be as high as USD 149 per ton of fiber (up to 20% fiber reduction without adverse effects on paper's strength) depending on the cost of papermaking fibers. It was also determined that better performance in terms of strength development associated with a higher degree of MNFC fibrillation offset its high manufacturing cost. However, there is a limit from which additional fibrillation does not seem to contribute to further strength gains that can justify the increasing production cost. Further research is needed regarding raw materials, degree of fibrillation, and combination with polyelectrolytes to further explore the potential of MNFC for the reduction of weight of paper products. Keywords: Micro- and nanofibrillated cellulose (MNFC); Microfibrillated cellulose (MFC); Nanofibrillated cellulose (NFC); CNF; CMF; Tensile strength; Fiber reduction; Light-weight paper; Paper products; Retention aids; Cellulose fibers Contact information: a: Department of Forest Biomaterials, Science and Engineering, P. O. Box 8005, North Carolina State University, Raleigh, NC 27695-8005 USA; b: Department of Bioproducts and Biosystems, School of Chemical Engineering, Aalto University, Espoo, 02150 Finland; * Corresponding author: [email protected]INTRODUCTION The global trend toward digitalization has caused a decline in the consumption and production of printing and writing paper grades. Such reduction has been reported to be approximately 15% across the last 10 years with a forecasted drop of 4% over the next five years. Recycled fibers, more specifically “mixed office waste (MOW)” and “white office ledger (WOL)”, are the most used recycled fibers in the hygiene tissue industry (De Assis et al. 2018b). As digitalization continues to force a reduction in production of printing and writing papers, less MOW and WOL are available to produce recycled paper grades. This disruption in fiber supply has resulted in huge increases and fluctuations in fiber prices (Fig. 1). Not only has the availability of fiber been decreasing, but the quality of the fiber that is available has been continuously decreasing as well, resulting in weaker paper. Decrease in paper strength is a major concern since quality standards are rising (RISI
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PEER-REVIEWED REVIEW ARTICLE bioresources.com
Zambrano et al. (2020). “Nanocellulose & grammage,” BioResources 15(2), Pg#s to be added. 1
Using Micro- and Nanofibrillated Cellulose as a Means to Reduce Weight of Paper Products: A Review
Franklin Zambrano,a Heather Starkey,a Yuhan Wang,a Camilla Abbati de Assis,a
Richard Venditti,a Lokendra Pal,a Hasan Jameel,a Martin A. Hubbe,a Orlando J. Rojas,b
and Ronalds Gonzalez a,*
Based on publications related to the use of micro- and nanofibrillated cellulose (MNFC) in papermaking applications, three sets of parameters (intrinsic and extrinsic variables, furnish composition, and degree of dispersion) were proposed. This holistic approach intends to facilitate understanding and manipulation of the main factors describing the colloidal behavior in systems comprising of MNFC, pulp fibers, and additives, which directly impact paper product performance. A preliminary techno-economic assessment showed that cost reductions driven by the addition of MNFC in paper furnishes could be as high as USD 149 per ton of fiber (up to 20% fiber reduction without adverse effects on paper's strength) depending on the cost of papermaking fibers. It was also determined that better performance in terms of strength development associated with a higher degree of MNFC fibrillation offset its high manufacturing cost. However, there is a limit from which additional fibrillation does not seem to contribute to further strength gains that can justify the increasing production cost. Further research is needed regarding raw materials, degree of fibrillation, and combination with polyelectrolytes to further explore the potential of MNFC for the reduction of weight of paper products.
Keywords: Micro- and nanofibrillated cellulose (MNFC); Microfibrillated cellulose (MFC);
Zambrano et al. (2020). “Nanocellulose & grammage,” BioResources 15(2), Pg#s to be added. 2
2017). Papermakers tend to redress this situation by using expensive fibers that are better
quality than the low-cost alternatives. Some even resort to the use of synthetic additives,
which results in increased costs per ton of finished product. To meet market expectations
regarding paper strength, mechanical refining of recycled and virgin fibers is a common
practice in the industry (Hubbe 2007a). However, in the case of tissue products, even
though refining helps to develop fiber and web strength, at the same time it makes the sheet
denser and more rigid, which negatively affects water absorbency, bulk, and softness of
the tissue sheet, which are key properties of the final product (Kullander et al. 2012).
Fig. 1. Historic fiber cost data for major grades of recycled and virgin fibers: BEK: bleached Eucalyptus kraft; SBSK: southern bleached softwood kraft; SBHK: southern bleached hardwood kraft; DIP: deinked pulp; graph generated with data collected from Fastmarkets RISI (2017)
There is a pressing need to develop new technologies to face current and future
market challenges related to fiber supply, quality, and cost while meeting changes in
consumption patterns. Micro- and nanofibrillated (MNFC) has emerged as a promising
candidate to generate either high-value applications or low-cost alternatives. Thus far,
available reports have been focused on the improvement in tensile strength by addition of
MNFC in paper furnishes (Eriksen et al. 2008; Taipale et al. 2010; He et al. 2017). This
might be mainly beneficial for poor quality furnishes composed of recycled fibers, where
strength properties of such fibers can be insufficient to meet specifications of a paper grade.
However, for paper products where strength is not an issue, consumers are not willing to
pay a premium for a product that has a superior strength (De Assis et al. 2018a). Therefore,
in such cases it makes more sense to consider the gains in strength obtained by MNFC to
reduce the fiber content of the paper product instead of merely developing excess strength.
This strategy could potentially allow the production of a lighter-weight version of
commercially available papers with properties that are consistent to those available in the
market but at a lower manufacturing cost. Moreover, a more rapid adoption of the
nanomaterial by the industry can be stimulated given the possible overall economic gain
offsetting the high perceived cost of MNFC.
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Acknowledging this opportunity, the main goal of this work is to review what is
known about factors that affect the ability of highly fibrillated cellulosic materials, such as
MNFC, to provide strength and possibly to allow for reductions in the basis weight of
various paper products. To accomplish that goal, this review will begin by examining
background information concerning nanocellulosic materials and their application in
papermaking. To this end, a holistic approach will be used to provide readers with an
effective means to rationalize the main variables affecting the performance of MNFC in
paper furnishes. Identification of knowledge gaps as potential areas for further research
will be emphasized. When considering the factors affecting paper strength – with attention
to how the usage of MNFC can augment paper strength – it will be argued that some of the
key challenges in research, up to this point, have involved uncertainties concerning the
retention of MNFC. Another key challenge, especially when attempting to compare results
of different studies, is that chemical aids intended to retain MNFC in the paper may also
affect fiber network formation, and therefore the strength of the sheet. After reviewing
these factors, two case studies will be considered to highlight economic considerations that
may be important relative to commercialization of MNFC as an additive for fiber reduction
in papermaking.
DIGGING INTO THE CELLULOSE STRUCTURE: NANOCELLULOSE
To enable a better understanding of the potential roles of MNFC as an additive in
paper grade applications, this section provides background about MNFC, including its
types, some aspects of its chemistry and morphology, and production.
Cellulose and Nanocellulose Cellulose is one of the most important renewable natural biopolymers and is almost
inexhaustible as a raw material (Siró and Plackett 2010; González et al. 2014). Wood is
the major source of cellulose, but other important natural sources where cellulose is
Degree of beating Fiber fibrillation and fines content*
Additives
Type of additive
Polyelectrolytes* (Carbohydrates, amides, amines, quaternary ammonium with cationic or anionic nature)
Fillers
Sequence of addition Pre-mixture of polyelectrolyte and MNFC or
direct addition of components into paper furnish*
Bulk pH Changes in pH and salinity of paper furnish
containing MNFC Salinity
Furnish Composition MNFC to additive ratio*
MNFC to pulp fiber ratio
Degree of Dispersion Degree of MNFC dispersion in paper furnish*
*: subjects discussed in this review
Intrinsic and Extrinsic Variables Fiber source
The type of fiber used for the production of the MNFC has an important influence
on the fibrillation development, fines generation, and subsequent performance of the
nanocellulosic material (Stelte and Sanadi 2009; Lahtinen et al. 2014; Johnson et al. 2016).
At similar levels of mechanical treatment, hardwood cellulose nanofibrils will produce a
comparable but slightly weaker film, i.e., lower tensile strength, than softwood cellulose
nanofibrils (Spence et al. 2010a,b). Thus, if the tensile strength of the resulting film is used
as an indication of the fibrillation degree induced by the treatment, hardwood cellulosic
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fibers are harder to fibrillate than softwood fibers; i.e., they will require a higher level of
pre-treatment and mechanical treatment (Stelte and Sanadi 2009; Vartiainen et al. 2015;
Zhao et al. 2017).
Figure 4 shows scanning electron microscopy (SEM) images comparing the
progression of hardwood fibrillation to the fibrillation of softwood fibers after a given
number of passes through a refiner. Similarly, when using CNF as an additive to hardwood-
based pulp handsheets, hardwood CNF produces lower tensile and internal bond values
compared to softwood CNF at a given fines content (< 86% fines). However, for fines
content above 90%, the change in the handsheets properties is independent of the source
used for the CNF production (Johnson et al. 2016).
Fig. 4. SEM images comparing the fibrillation evolution for hardwood and softwood fibers after a given number of passes through a refiner (adapted with permission from Stelte and Sanadi 2009; Copyright 2009 American Chemical Society)
Results from this work suggest that at the nanoscale, the expanded surface area
overcomes the chemical component inherent to the fiber source and that such surface area
can also drive interaction between the CNF and the fiber network. Further research to
assess the influence of different raw materials on the performance of nanocellulose when
used as a paper strength additive needs to be conducted.
The chemical composition of the pulp fibers also plays a key role in the fibrillation
process. A higher hemicellulose content facilitates the fibrillation of nanofibers during the
mechanical treatment of the pulp (Iwamoto et al. 2008; Spence et al. 2010a,b). Also, it is
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proposed that lignin-containing fibers promote fibrillation because of lignin’s antioxidant
properties and its ability to stabilize radicals generated from cellulose during the grinding
treatment (Ferrer et al. 2012; Solala et al. 2012). Results reported by Spence et al. (2010a,b)
support Ferrer’s 2012 finding that lignin-containing NFC produces films with comparable
properties to their bleached counterparts. Higher lignin content was found to aid in the
fibrillation process because the resulting nanofibrils have a higher surface area and lowest
size fraction (Imani et al. 2019b). Alternatively, it is suggested that the presence of lignin
and hemicellulose hinders the fibrillation process, especially when combined with TEMPO
pre-treatment (Herrera et al. 2018; Syverud et al. 2011). A high content of hemicellulose
may be detrimental for the fibrillation, as xylan does not have the C6 that is the oxidation
position targeted by the TEMPO catalyst (Syverud et al. 2011). It should be noted that the
studies cited here used different pulping processes, e.g., kraft, soda, semi-chemical, to
produce the unbleached fibers for MNFC production. Therefore, the discrepancies in
performance could be due to the different pulping environments influencing the remaining
lignin structure in the fibers. For example, during the kraft process sulfate groups will be
added to the lignin structure as it is being degraded, but the sulfate groups are not present
in the soda process. So far, studies have only concerned themselves with the amount of
lignin remaining with the cellulose before fibrillation, which makes it hard to draw a
conclusion on how the different degradations of the lignin structure influences fibrillation.
When evaluating papermaking applications, the blending of lignin-containing
nanocellulose into fiber sheets improves the overall strength profile; however, it has been
shown to be less efficient than using lignin-free nanocellulose (Osong et al. 2014). Before
reaching a definitive conclusion, more research should focus on how the presence of lignin
alters the performance and reinforcement capabilities of the MNFC in targeted
papermaking applications. For example, there is evidence suggesting that even though
lignin-containing MNFC could be suitable as a bulk additive in papermaking, it would
make a poor coating additive compared to lignin-free MNFC (Imani et al. 2019a).
Particle size (micro vs. nano) and degree of fibrillation
The size of fibrils and the degree of fibrillation, the latter referring to the
homogeneity of the fibrillated sample, largely determine the colloidal features of pulp
suspensions containing MNFC. The colloidal interactions exhibited by particles at the
micro- and nanoscale result from a balance between electrostatic and dispersion forces
governing the system. Any change in the degree of fibrillation contributing to increase the
surface area will also result in a higher surface charge, directly affecting the colloidal
behavior among cellulosic fibrils (Hubbe 2007b; Hakeem et al. 2015; Saarikoski et al.
2017).
The fibril size plays a key role in the resulting properties of paper when MNFC is
incorporated in pulp suspensions. The MNFC with a small particle size produces a paper
with greater bonding strength and denser structure, but it also results in lower retention. In
contrast, MFC with a broader particle size distribution shows less improvement in
mechanical properties but more efficient retention in the fiber web (Su et al. 2014). Madani
et al. (2011) reduced the average fibril length of MFC from 221 µm to 100 µm by applying
a gel fractionation technique. Composite papers formed by 10% addition of MFC to
chemical wood pulp showed 25% increase in tensile index for non-fractionated MFC and
an additional 10% improvement for fractionated MFC. Eriksen et al. (2008) also reported
an increasing tensile index in TMP paper by decreasing the average particle size of MFC.
However, the authors also claimed that mechanical processing beyond a specific energy
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consumption does not translate into a significant further increase in tensile strength. They
observed a drop in tensile index from a maximum value when the degradation of
homogenized MFC was successively increased beyond that point. From this study, it is
possible to infer that there is an optimal fibrillation degree that will yield a maximum
improvement in tensile strength. Any additional energy input beyond this limit will
represent an energy loss in the overall energy balance associated with MFC manufacturing.
In agreement with this logic, He et al. (2017) concluded that MNFC production should be
focused on tailoring the properties of the fibrillated fibers to be incorporated into a specific
application, i.e., achieving an optimal degree of fibrillation for a given application, rather
than trying to retrofit MNFC, whose dimensions are completely nanoscale, to possible
applications.
Fibrillation also has an important influence on the mechanical properties of
nanocellulose films. The NFC with a high degree of fibrillation can be more easily
dispersed in the bulk suspension prior to sheet formation. As a result, a more homogeneous
distribution of the defects and vulnerable locations for initiation of failure within the
network is obtained, which consequently improves the strength and rigidity of the
nanostructure (González et al. 2014). A reduction in the average fibril size also results in
more fiber bridging through both mechanical interaction and H-bonding. However,
excessive mechanical treatment has the potential to reduce strength properties due to a
possible reduction in the length of the fibrils (Stelte and Sanadi 2009).
The degree of fibrillation influences the dewatering capacity of pulp suspensions
and the solid content of the paper after wet pressing. He et al. (2017) described an increase
in the drainage time as a function of the degree of fibrillation of CNFs, which was
accompanied by an overall reduction in the degree of polymerization, zeta potential, and
degree of crystallinity. As the fibrillation of fibers progresses, particles are more easily
incorporated into the fiber web. However, this partially closes the pores between fibers,
limiting the ability for the wet web to drain water. The CNFs also hinder drainage due to
its increased water retention capacity, which may be the cause of the reduction in solids
content observed after wet pressing.
Besides favoring the reduction of the high-energy demand associated with
mechanical fibrillation processes, the pre-treatment of cellulose fibers also aims to improve
the achievable degree of fibrillation (Isogai 2013). Delgado-Aguilar et al. (2015) evaluated
the reinforcing ability of five types of CNFs prepared by different pre-treatments
(chemical, mechanical, and enzymatic) when combined with papermaking pulps. The
CNFs with a high degree of fibrillation and a large specific area, e.g., TEMPO-oxidized
CNF, showed the best performance as paper strength additives. However, it was shown
that CNFs with a smaller degree of fibrillation could also induce an equivalent increase in
the mechanical properties by using a higher load compared to that of TEMPO-oxidized
CNFs. A similar observation was made by Johnson et al. (2016), who claimed that similar
values of paper strength could be reached by either adjusting the CNF loading level or the
CNF fines content. As shown in Fig. 5, the authors found that changing the fines content
in the CNF from 77% to 94% did not affect the performance in terms of tensile index. This
held at all the levels tested for CNF load in the handsheets. The findings also support the
idea that there are diminishing returns in strength improvements past a certain MNFC
degree of fibrillation.
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Fig. 5. Effect of addition of CNF with different fines content on the tensile index of handsheets (no retention aids were used) (adapted from Johnson et al. 2016)
Degree of Beating of Papermaking Fibers Fibrillation and fines content
Mechanical refining of papermaking fibers increases the number of fiber-to-fiber
bonds, thus producing a stronger paper. The mechanisms of shearing and compression
forces involved in this process completely transform the original characteristics of the
fibers. The increase of external fibrillation enlarges the fiber surface area and creates fibrils
from the primary and secondary wall. Fines are also produced when the primary and
secondary wall fibrils are cut off from the fibers (Smook 2016). These factors might affect
the reinforcing features of the MNFC due to a change in the interaction with the pulp fibers
in suspension and during the sheet formation.
Several authors have suggested that an increase in the external fibrillation of pulp
fibers inhibits the enhancement that MNFC has on fiber-fiber bonding. Su et al. (2013)
compared the strength development resulting from the blending of MFC with unrefined
fibers and fibers refined at 10,000 rpm in a PFI mill. The addition of MFC into unrefined
fibers resulted in a radical increase in the dry strength in contrast to the dry strength of
composites made from the mixture of refined fibers and MFC, which exhibited a small
variation despite the MFC content added. Afra et al. (2013) evaluated the effect of NFC
addition on the properties of paper made from softwood pulps beaten to 350 and 550 CSF.
As a recurrent trend, the increase in the tensile strength of the paper prepared with 550 CSF
softwood fibers was greater than the increase obtained with the 350 CSF fibers (~72% vs.
~60%).
González et al. (2012) studied the physical, morphological, and mechanical
properties of paper sheets reinforced with TEMPO-oxidized NFC using unbeaten and
slightly beaten Eucalyptus slurries. An analysis of that study conducted by Boufi et al.
(2016) showed that an addition of 3 wt% NFC produced an increase of approximately 24%
in the tensile index, which was similar for both beaten and unbeaten pulps. Conversely,
after addition of 6 wt% NFC, the increase in tensile index shown by the unbeaten pulp was
67% while only a 45% increase was obtained for the slightly beaten pulp. A similar trend
was found by Taipale et al. (2010). The authors obtained increments of 73% and 35% in
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tensile index of the paper after adding NFC to a softwood pulp beaten for 10 and 30 min.
In this case, a cationic starch dosage of 15 mg/g dry pulp was used.
The presence of fines in pulp fibers might also affect the MNFC performance when
added into pulp furnishes. Potulski et al. (2014) reported an increase of 258% in tensile
index after the incorporation of microfibrillated cellulose to bleached Eucalyptus pulp with
a low refining level (15° SR), compared to an increase of 41% obtained after adding an
equivalent amount of MFC to the same pulp but at a higher degree of refining (25° SR).
The authors ascribed the difference observed to the fact that the combination of refining
and addition of MFC generates a larger number of fines in the system that imposes limits
on increasing the tensile strength of paper. Furthermore, after examining the work by
González et al. (2013) covering the effect of the combination of enzymatic treatment (bio-
refining) and NFC addition on the mechanical properties of paper, Boufi et al. (2016) stated
that González’s study supports the theory that the fibrillation of refined pulps is the variable
limiting the performance of NFC in papermaking. This is because the bio-refining process
does not generate the amount of fines that is typically generated during the traditional pulp
refining. It has been also reported that the presence of fines negatively impacts the drainage
properties of pulp suspensions containing MFC, even with the presence of cationic
polyelectrolytes. Taipale et al. (2010) showed that after removing the fines from a beaten
pulp suspension (the pulp was beaten for 60 min), the drainage of the furnish depended less
on both the MFC content and type of polyelectrolyte used.
The results just discussed reinforce the hypothesis postulated by Brodin et al.
(2014) that CNF shows its best performance in fiber networks where poor fiber bonding is
the variable hindering the tensile strength. For that reason, the addition of MNFC in paper
furnishes comprised of beaten chemical pulps is less likely to significantly enhance the
mechanical properties of paper sheets in comparison to the addition in unbeaten pulp
furnishes. It is also worth noting that although the percentage of change in tensile index
decreases with the fiber fibrillation, the tensile index value obtained by combining
defibrillation of pulp fibers and MNFC addition is greater compared to that obtained when
MNFC is simply added to a pulp slurry of unbeaten fibers.
Despite seeing a better MNFC performance when adding it to unbeaten furnishes,
several authors have stated that the gains in tensile index obtained by the addition of MNFC
to a pulp furnish are similar to what could be obtained by beating the original pulp
suspension before the sheet formation. Sehaqui et al. (2013) studied the mechanical
properties of handsheets made of 10% NFC and 90% softwood pulp fibers subjected to
varying levels of beating. The authors reported that the addition of NFC to non-beaten pulp
fibers had a similar effect on tensile index as beating a 100% softwood fiber furnish
because both strategies resulted in a high-density sheet. Hollertz et al. (2017) described the
same trend for unbleached kraft pulp sheets containing either carboxymethylated CNF or
kraft MFC with different loadings. However, that relationship between tensile strength and
density was not found when chemically modified CNFs (periodate-oxidized CNFs and
dopamine-grafted CNFs) were introduced into the paper furnish using polyvinyl amine
(PVAm) as a retention aid, as shown in Fig. 6a. In this case, the tensile strength was
significantly above the beating curve. Taipale et al. (2010) also stated that the results
obtained through the addition of MFC without cationic starch considerably mimicked the
results obtained with simply beating the bleached softwood kraft pulp and using no MNFC.
As shown in Fig. 6b, slightly higher tensile strength values were attributed to the MNFC
with more fibrils compared to the fibrils present on fibers generated during the beating
process. Nevertheless, the combination of carboxymethylated MFC and cationic starch
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significantly increased the tensile strength compared to the tensile strength seen with just
the beaten fibers at the same drainage rate. The underlying mechanisms yielding these
results are discussed in the following section of this review.
Fig. 6. Comparison between addition of MNFC and mechanical beating of pulp fibers as strategies to increase the tensile index of paper sheets: (a) different types of chemically modified CNFs added to a 4000 PFI-revs beaten pulp using 2.5 mg/g PVAm as retention aid or, if indicated, polyDADMAC; (b) different types of MFCs added to a 10 min beaten pulp using 15 mg/g of cationic starch (CS) as fixative. F4 and F10 indicates that the pulp was passed through a fluidizer unit either four or ten times respectively. CMMFC is a carboxymethylated MFC sample (adapted from Taipale et al. 2010; Hollertz et al. 2017)
Type and Addition Point of Additive Polyelectrolytes
Polyelectrolytes showing diverse chemical nature and surface charge density are
commonly introduced in the pulp slurry to improve the retention of fines particles during
sheet formation. Using polyelectrolytes, best-known as retention aids (RA) and dry
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strength agents (DSA), is considered a proven strategy in conventional paper machine
operations. Retention aids represent one of the most suitable ways that researchers are
currently focusing on to increase the retention of MNFC in the sheet. In this sense, factors
related to the chemical structure of the polyelectrolyte, bulk concentration of both MNFC
and retention aids, as well as the sequence of addition, are main variables affecting the
system performance.
The typical chemical species studied for their use as retention aids and possibly as
dry strength agents are long molecular chain polymers with a cationic nature. Four main
families of polyelectrolytes used in combination with MNFC have been identified: (i)
carbohydrates, e.g., cationic starch (CS), xyloglucan, and chitosan (CH); (ii)
polyvinylamines (PVA); (iii) polyacrylamides, e.g., c-PAM, c-PAM-B; and (iv) cationic
polymers with quaternary ammonium, e.g., polyamidoamine-epichlorohydrin (PAE)
(Boufi et al. 2016).
The chemical structure of the cationic polymer will influence the way MNFC
interacts with it, i.e., the balance between non-electrostatic forces, electrostatic forces, and
flocculation mechanism. The use of MNFC in pulp slurries containing polyelectrolytes has
been shown to increase the flocculation and stability of the particle flocs. MNFC increases
the floc stability in the presence of CS due to the formation of hydrogen bonds, regulates
the negative effect of increasing PAM dose on floc stability, and increases the floc size
when combined with PVA. Therefore, the particular interaction between MNFC and the
cationic polymer will be the crucial factor affecting the retention of the nanoparticles within
the fiber network (Merayo et al. 2017a). Besides improving retention, some
polyelectrolytes can also boost the strengthening effect of MNFC by generating synergic
effects within the paper web. The most important strength improvements reported in the
literature correspond to cases where MNFC has been combined with a polyelectrolyte
(Ahola et al. 2008; Taipale et al. 2010; Boufi et al. 2016; Hollertz et al. 2017; Rice et al.
2018; Yousefhashemi et al. 2019). Moreover, the use of retention aids has been shown to
improve the dewatering of pulp suspensions containing MNFC (Merayo et al. 2017b).
These synergistic behaviors will only occur if the correct retention aid chemistry for a
system is implemented.
Merayo et al. (2017b) studied possible synergies between MFC and RAs to improve
recycled paper strength while avoiding negative effects on the drainage process. Five
different RAs were considered: PVA, CH, CS, c-PAM, and c-PAM-B (which is formed by
a formulation of polyamine as coagulant, PAM, and hydrated bentonite clay). As a
common feature, all the RAs improved water drainage and retained approximately 90% of
the solid particles. A comparison made at the lowest dose tested, which was representative
of the dosages used in industrial applications, showed that c-PAM and c-PAM-B were the
most efficient in reducing drainage times, followed by CH. The PVA also provided good
results with a dosage ten times higher than commercially viable doses. The CS was the
least effective in reducing drainage times, especially at low and moderated doses.
Regarding mechanical properties, the addition of MFC using c-PAM-B resulted in
the best formation uniformity of the paper and the higher tensile index increase (15%).
According to the authors, bentonite, an anionic component found in this RA, kept a good
dispersion of MFC in the pulp despite the presence of PAM, which is known for promoting
a high floc formation. No synergy was observed between MFC and c-PAM. The highest
values of tensile index were obtained with pulp containing 1% MFC when CH was used as
RA. The CH itself did not affect tensile index; however, in combination with MFC, a
synergistic effect developed, enhancing the paper strength. The use of MFC and PVA
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provided a tensile increase of 15% at its highest point, and for the case of CS, addition of
MFC showed a negative synergy that decreased the tensile index. The authors claimed that
CS might be interacting with MFC in the pulp, resulting in flocs that favor retention but
worsen formation uniformity. At the same time, this might decrease the interaction between
MFC and fibers. From this study, it is important to note that some RAs required the addition
of MFC to the pulp to recover the tensile index that the paper originally shows without the
presence of any additive. For example, c-PAMs provided the lowest drainage time at
expenses of a high floc formation, which favors faster drainage but hinders fiber bonding.
Thus, a balance between flocculation and bondability will also be required in this case, and
attention needs to be taken when dealing with additives exhibiting such features.
Similarly, Taipale et al. (2010) studied the effect of the addition of MFC and fines
on the drainage of a kraft pulp suspension and its relation with paper strength. Five
polyelectrolytes were evaluated for this purpose: three different types of c-PAM,
polyDADMAC, and CS. First, contrary to the results obtained by Merayo et al. (2017b),
an increase in the drainage time was obtained in the presence of c-PAM and MFC.
According to the authors, high molar mass c-PAMs tend to form a thick, loose, and
viscoelastic layer with the added MFC that might increase the water retention capacity of
the network. Secondly, compacted networks formed by the addition of polyDADMAC
allowed faster drainage as the low molar mass high charge density polyelectrolyte adsorbs
in a flat conformation leading to thinner layers of polymer and MFC. Finally, highly
branched CS with a very high molecular mass only slightly decreased the drainage. The
authors reported a strong dependence between the type of polyelectrolyte and the drainage
for suspensions containing fines. As a common trend, it was stated that addition of MFC
causes an increase in the strength of the paper, which can be enhanced when CS is used as
a fixative. Although a reduction in the drainage rate consistently accompanied this effect,
the authors also found that by adding carboxymethylated MFC in combination with CS it
was possible to double the tensile strength without decreasing the drainage rate. They
attributed this finding to the small size and high-density charge of the anionic MFC that
would allow the formation of a thin MFC layer on the CS previously adsorbed onto the
fiber surface. As a result, MFC nano-networks would be coating the fibers rather than
filling the voids between them, leaving more open pores for water to freely drain from the
sheet.
Likewise, Hollertz et al. (2017) showed how cellulose micro- and nanofibrils
exposed to different chemical modifications can be effectively used as strengthening
additives in papermaking. The authors considered carboxymethylated CNFs as the starting
reactant to produce two types of modified CNFs: periodate-oxidized carboxymethylated
and dopamine-grafted carboxymethylated. These three different CNF were added to a pulp
suspension of unbleached kraft pulp with and without PVAm used as a retention aid. In
this case, an increase in the tensile strength index of 56% was obtained with as little as 2
wt% periodate-oxidized CNF added. The authors found that PVAm promotes the
adsorption of periodate-oxidized CNF on the fiber surface before dewatering rather than
its attachment in the pores between the fibers during dewatering. As a result, a higher
dewatering rate was obtained for periodate-oxidized CNF compared to that of the sheets
prepared with dopamine-grafted CNF and a conventional kraft MFC. This coating-like
conformation is similar to the one reported by Taipale et al. (2010) for sheets made with
the addition of carboxymethylated CNF in combination with CS. Therefore, based on the
results obtained from the previous studies, it is possible to state that retention aids affect
the conformation of the fibrillated material onto the cellulosic fibers, and the resulting
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arrangement is what will dictate the extent of improvement in strength and drainage rate
obtained in the paper product.
The formulation and addition of cationic polyelectrolyte complexes (CatPECs)
onto papermaking furnishes containing MNFC, as well as the pretreatment of the
nanofibers with cationic polymers, has also been explored. Schnell et al. (2019) evaluated
the efficiency of PECs to improve the reinforcing capacity of lignocellulosic
micro/nanofibers (LCMNF) while reducing the drainability problems caused by the
fibrillar material. CatPECs were prepared by mixing polyacrylic acid with poly(allylamine
hydrochloride). The combination of CatPECs with LCMNF increased the tensile strength
of the paper sheet compared to a reference sheet with no additives. The highest
improvement (+48%) corresponded to the CatPEC dosage required to reach the charge
neutrality of the system (0.75% based on pulp) in a papermaking furnish containing 3%
LCMNF. At this dosage, the negative effects on drainage caused by the LCMNF were
minimized, and the retention of fines and LCMNF were maximized as determined by the
Britt Dynamic Drainage Jar test.
Rice et al. (2018) evaluated the performance of NFC pretreated with cationic starch
as a bonding system in 350 g/m2 handsheets made from bleached kraft pulp (70% hardwood
and 30% softwood). NFC pretreated with cationic starch was particularly effective in
improving the tensile strength and stiffness of low-refined pulp mixtures (473 mL CSF)
compared to high-refined pulp mixtures (283 mL CSF). Such a strategy allowed improved
tensile strength at a lower apparent density (higher bulk) of the handsheets, which the
authors suggest could be used as a means of substituting the mechanical refining of the
pulp mixture in preparation of specific paper grades. It was proposed that cationic starch
enhances the retention of NFC in the paper web and NFC simultaneously acts as an
extender for cationic starch, which results in a synergistic action that improves paper
strength. At the same time, a “spring-back” effect of the NFC-starch complex due to the
elastic character of NFC might help to regain bulk of the paper web after wet-pressing
(Hubbe 2019). Additional treatment of the cationic starch-treated NFC with colloidal silica
was also employed to promote better dewatering of the pulp slurry.
Sequence of addition
The colloidal behavior of systems comprising MNFC, pulp fibers, and
polyelectrolytes might be sensitive to the sequence used to introduce each substance into
the pulp suspension. However, not many systematic studies assessing the influence of the
addition strategy on the final properties of paper have been published. Ahola et al. (2008)
studied the differences in addition strategies of CNF and PAE onto cellulose fibers.
According to the sequence of addition considered, two configurations were obtained: a bi-
layer system for the case where CNF was added to pulp suspension containing the retention
aid and nano-aggregates when the CNF was pre-flocculated with the retention aid and then
added to the pulp suspension. The adsorption of PAE and nanofibrils as a layer-structure
translated into a significant increase in both dry and wet tensile strength of paper.
Conversely, cationic aggregates did not significantly improve the paper strength properties.
He et al. (2017) investigated the effect of the addition method of cellulose nanofibrils into
the wet-end of the papermaking process. Two different addition strategies were assessed:
a precipitated calcium carbonate (PCC)-CNF composite filler and a wet-end additive. CS
and c-PAM were used to promote binding and improve retention. Handsheets dosed with
the composite filler showed a higher solid content than the CNF-added sheets after wet
pressing; however, in both cases, a similar tensile strength was obtained.
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Furnish Composition MNFC to polyelectrolyte ratio
Taipale et al. (2010) reported a linear increase of tensile index with increasing
addition of MFC in a pulp suspension containing cationic starch. Conversely, Merayo et
al. (2017b) found a decrease in the tensile index with increasing addition of MFC to pulp
slurries containing CH, CS, and PVA as retention aids. Moreover, increasing the
concentration of retention aid did not cause significant improvements in the tensile index,
which even decreased in some cases. For these systems, the results suggest that retention
of MFC is not the variable driving the decrease in tensile strength. According to the authors,
high concentrations of MFC do not necessarily increase paper strength as the effect of poor
paper formation can overcome the reinforcing capacity of MFC. Similarly, Hollertz et al.
(2017) stated that retention aids do not significantly increase the fibril content in handsheets
prepared using chemically modified CNF and PVAm as a retention aid. The authors rather
attributed the self-retention capacity shown by these CNFs to their large size and a high
degree of aggregation.
Degree of Dispersion Degree of MNFC dispersion in the paper furnish
There is a proportional correlation between the dispersion degree of the species in
a pulp suspension and the mechanical properties of the resulting paper sheets. Especially,
for colloidal systems comprising MNFC, pulp fibers, and polymers, the energy input
provided by hydrodynamic shear will affect the dispersion and thus the distribution of each
component within the fiber matrix (Alcalá et al. 2013; Campano et al. 2018). Given the
viscous features of the gel in which nanocellulose is normally produced, its
homogenization in aqueous medium proves more difficult compared to cases where there
is a dilute dispersion of nanofibers (Osong et al. 2016). Furthermore, as the tensile strength
of a paper sheet depends mostly on the weakest bonds in the fiber network, a poor
distribution of MNFC in the pulp furnish will translate into a non-optimum performance
of the fibrillated component when used as a paper strength additive.
Based on this logic, Alcalá et al. (2013) studied the effect of the number of
revolutions applied during dispersion on the performance of NFC within an unbleached
Eucalyptus fiber matrix. The authors found a gradual decrease in porosity and a linear
evolution of density with the addition of NFC. Nevertheless, after achieving the highest
increase of density corresponding to samples with 9 wt% NFC, further addition caused a
drop in these properties, as shown in Fig. 7a. The authors claimed that an increase in the
NFC content in the paper slurry requires higher energy input to promote a homogeneous
dispersion and result in a denser composite with a better interaction between the nanofibrils
and the larger fibers. This hypothesis was corroborated after dispersing fiber slurries
containing 3 wt% NFC at different revolutions. Figure 7b shows that there was an increase
of 18% in tensile strength when the number of revolutions was increased from 180,000 to
240,000. The authors stated that above 3 wt%, properly dispersion of NFC is one of the
key factors to boost the reinforcing capacity of the material for composites manufacturing.
In a similar effort, Campano et al. (2018) studied the mechanical and chemical
dispersion of cellulose nanofibrils to improve its reinforcing effect on recycled paper. For
the experimental conditions, the amount of CNF was fixed at 1.5 wt%, and c-PAM and CH
were selected as retention aids. The authors reported an increase of approximately 9% and
approximately 15% in tensile index when the pulping time of the recycled pulp mixed with
CNF was increased from 10 min (30,000 revs) to 60 min (180,000 revs) using c-PAM and
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CH, respectively. A significant decrease in porosity accompanied this increase. According
to the authors, porosity is one of the signs that indicate a homogeneous dispersion and
higher retention of the CNF within the fiber network. It was also determined that the
temperature used during pulping (referring to pulping as pulp disintegration) does not have
any effect on the dispersion of the CNF, as similar results in tensile index were obtained
for 20 °C and 50 °C for the same pulping time.
Fig. 7. Evolution of physical and mechanical properties of unbleached Eucalyptus pulp: (a) reinforced with different contents of NFC dispersed at 180,000 revolutions; (b) reinforced with 3 wt% NFC using a different number of revolutions for dispersion (adapted from Alcalá et al. 2013)
Finally, the combination of dispersing agents in low concentrations (0.003%) with
the CNF allowed a reduction in the pulping time. This result was attributed to more
effective dispersion of the CNF; however, the increase in the tensile index from shorter
pulping times was not as large as the increase obtained with longer pulping times (20.6%
versus 30.0%). Ultimately, the dispersion strategy to implement in each process will
depend on practical considerations. The mechanical properties of paper sheets reinforced
(b)
(a)
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with MNFC depend not only on the combination of intrinsic and extrinsic variables and
the furnish composition discussed in the previous sections. The influence of the degree of
dispersion of the papermaking furnish also plays a fundamental role before the formation
of the paper sheet. Therefore, as mixing of the MNFC with the larger fibers is a required
step for fabrication of composites, taking advantage of this process could result in more
efficient use of the nanocellulose. Currently, there are different approaches applied in the
industry to increase the mechanical properties of paper. Many of them consist of modifying
raw materials, which greatly increase the production cost. However, a clear understanding
of the effects that mixing has on the distribution of the MNFC into a fiber furnish could
allow papermakers to obtain outstanding results by changing the mixing process rather than
modifying the raw materials. As an example, the basis weight, which is a critical variable
contributing to the mechanical resistance of the paper sheet, could be easily reduced and
the losses in paper strength could be compensated with the addition of MNFC under the
proper mixing conditions.
ECONOMIC POTENTIALS OF MNFC AS A DRIVER FOR FIBER REDUCTION
What Is the Paper Strength Expected by Consumers? There are at least three main influencers on paper strength: (i) individual fiber
strength and their arrangement in the sheet, (ii) the intensity of the fiber-fiber bonds, and
(iii) aspects of the feedstock raw material, such as fiber length distribution (Ankerfors et
al. 2013). Additionally, as already discussed, the uniformity of formation within the paper
sheet also can profoundly affect paper strength. Long fibers generally produce a sheet with
a higher tensile strength compared to short fibers (Page 1969), which is because they have
more sites to bond with multiple fibers. Paper is stronger in the machine direction than the
cross-direction due to fibers preferentially arranging themselves lengthwise in the machine
direction. Ultimately, tensile failure of paper occurs because of the interaction between
interfiber bonding and fiber failure. Products, such as printing and packaging grades, have
well developed fiber-to-fiber bonds, and it is expected that the sheet will fail due to broken
fibers. Page’s famous 1969 theory proposes that while the sheet is under a load, fiber bonds
will start to fail. As the fiber bonds start to fail, there will be fewer bonds in the rupture
region to disperse the load, causing individual fibers to take on more load until reaching
their rupture strain. Tissue grades have relatively weak fiber-to-fiber bonds, which will
cause the sheet to fail due to the breaking of fiber-to-fiber bonds instead of the breaking of
individual fibers.
The strength requirements of paper products depend on the grade and final
application. For printing and writing grades, tensile strength is needed to feed the sheet
through the printers. Similarly, for tissue paper tensile strength is needed to withstand strain
and stresses in the tissue machine and converting operation. The challenge with tissue is
that most of the things that are done to help improve tensile strength hinder other desirable
properties such as bulk and softness. Although a reduction in the tensile strength will
improve the bulk and softness of the tissue sheet, if the tensile strength is too low, then the
sheet will not support itself on the paper machine (De Assis et al. 2018b). In packaging
grades, paperboard strength (usually ring crush or burst) is critical because all
containerboards are rated for a certain cargo loading.
The easiest way to produce a stronger sheet of paper is to add more fiber to prepare
a unit area of paper sheet (increase in basis weight). End-use customers are not concerned
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with how much fiber is used to produce their paper; they are mainly concerned with the
final paper strength (along with softness and bulk for tissue grades). This can be seen with
the use of filler in printing and writing grades. Fillers are significantly cheaper than fiber
so companies use as much filler as they possibly can without negatively impacting the
paper properties (He et al. 2017). This fulfills the customer’s expectation while keeping
the cost as low as possible, which translates into a higher profit margin. It has been shown
that by introducing MNFC into a papermaking furnish, the strength properties of the paper
can be increased. However, customers generally are not willing to pay a premium for an
enhanced strength (De Assis et al. 2018a). As an alternative, the authors of this review
suggest it is more feasible to change the mindset from using MNFC to improve the strength
properties of commercially available papers to using MNFC to produce a lighter-weight
version of these papers (keeping all the properties consistent to what is currently on the
market) by reducing the overall fiber content. This is in agreement with the trend in
papermaking of reducing fiber (Retulainen and Nieminen 1996) and, at the same time,
should allow for a more rapid introduction of the MNFC into the industry.
Case Study: Reducing the Grammage of Unrefined Hardwood Chemical Fiber Sheets
This section intends to demonstrate the potential savings obtained from the
grammage reduction driven by the addition of NFC to paper sheets having a target tensile
strength. The analysis is based on experimental data presented by Hamann (2011), who
studied the effect of grammage reduction for sheets prepared with unrefined hardwood
chemical pulp with 10% addition of NFC, as shown in Fig. 8. In a parallel study, the author
tested the effect of different NFC loads on the tensile strength of 60 g/m2 sheets. These
results, indicated by the colored dots in Fig. 8, were added to the original chart.
Fig. 8. Grammage reduction is driven by the addition of NFC. Note that the same tensile strength is reached by using different combinations of grammage and NFC load (adapted from Hamann 2011)
For the analysis, an 80 g/m2 sheet without NFC, with a tensile strength of 26.2 N,
was selected as the base case. The authors found a strong linear correlation between the
grammage and the tensile strength with and without NFC (R2 equals to 1.00 and 0.99,
respectively). Therefore, it was assumed that there is not a strong dependence between the
rate of change in the tensile strength per grammage unit and the NFC load used.
Considering the slope of the dataset with 10% NFC, the tensile strength was extrapolated
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for each NFC load in the 60 g/m2 sheet to reach a value of 26.2 N. As a result, it was
possible to obtain paper sheets with different grammages and NFC loads exhibiting the
same tensile strength value. The results are shown in Fig. 8.
Figure 9 shows potential cost reduction driven by the addition of NFC for both
recycled and virgin fibers. The grammage reduction was calculated considering the amount
of fiber that is possible to reduce for the different NFC-grammage combinations obtained
from Fig. 8. The cost reduction was assessed as the difference between the US dollars per
metric ton of dry pulp saved and the US dollars associated with the NFC load required to
deliver the target tensile strength value. Two cost references (low and high) were selected
to evaluate the sensitivity of the fiber cost on the cost reduction. These values, USD 820
and USD 1,100 per ton of fiber respectively, were taken from the RISI database and
correspond to the lowest and highest cost of northern and southern mixed bleached
hardwood kraft (Canadian/US) between December 2016 and April 2018 (Fastmarkets RISI
2017). The cost per dry ton of NFC considered was USD 1,493. This value corresponds to
an MNFC manufacturing facility that is co-located within a mill that produces northern
bleached softwood kraft (NBSK) pulp (De Assis et al. 2017).
Fig. 9. Potential cost reduction per ton of fiber driven by the addition of NFC. The gray dotted line indicates the % of grammage reduction that can be obtained by adding the indicated NFC load. The orange and blue dotted line show how such cost reduction would translate in USD savings per ton of fiber depending on the fiber cost. Low and high fiber cost are estimated to be USD 820 and USD 1,100 per ton of fiber respectively. The cost per dry ton of NFC considered was USD 1,493 based on the study published by De Assis et al. (2017)
Figure 10 shows that loads of NFC as low as 1 wt% already drive cost reduction.
The CNF load that maximizes the cost reduction depends on the cost of the fiber used for
the furnish preparation. For the low fiber cost, this load is around 6 wt%, whereas for high
fiber cost there is no maximum within the range studied. As the cost of the raw material
increases, savings due to cost reduction are higher. In this study, cost reduction can be as
high as USD 77 and USD 149 per ton of fiber for low and high fiber cost, respectively.
Cheaper fibers, i.e., recycled fiber, will have a more restricted range of operation before
the addition of MNFC becomes economically infeasible.
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Although the numbers shown in this study seem promising, additional aspects need
to be considered before such an operation can be scaled-up. First, this analysis is based
only on the tensile strength. A reduction in the grammage deteriorates almost all paper
properties, including those indexed by the basis weight (Retulainen and Nieminen 1996).
Thus, an integrated analysis considering the lowest acceptable basis weight according to
the paper grade produced needs to be considered. Second, Hamann (2011) reported a 50%
retention of NFC, and no retention aid was introduced in the paper furnish to improve this
value. If retention is less than 50%, using up to 6 wt% NFC might cause problems in the
runnability of the paper machine. On top of a negative impact on dewatering, a potential
build-up of NFC in the closed loop of the paper machine could increase the viscosity of the
recirculating water, making the operation impractical. At the same time, filling of wet-press
felts in the paper machine with unretained NFC may also represent an aspect of potential
concern due to its difficult removal by conventional treatments. This highlights the need
for carrying out an integrated analysis to study the feasibility of the use of MNFC to reduce
the fiber content.
Determining the Trade-off Between the Degree of Fibrillation and Load when Using MNFC as a Paper Strength Additive
From the previous discussion, one can expect there to be a fibrillation threshold
(optimum degree of fibrillation) from which any further mechanical treatment does not
translate into a significant increase in the mechanical properties of the paper. Moreover, a
trade-off between the degree of fibrillation and the nanocellulose load required to achieve
a target tensile strength value has been reported in the literature (Delgado-Aguilar et al.
2015; Johnson et al. 2016). From this situation, two possible scenarios can be developed:
(i) a small load of MNFC is required at the expense of a high degree of fibrillation (small
particle size) or (ii) a small degree of fibrillation (high particle size) is required at the
expense of a high load of MNFC. In this sense, when using MNFC as a paper strength
additive, the question of what the most profitable scenario is arises. This highlights the
importance of understanding the role of the particle size (micro versus nano) and degree of
fibrillation in the nanocellulose performance.
Case Study: Increasing in 10% the Tensile Strength of a Hardwood Sheet Using Softwood CNF
This section intends to estimate a feasible combination of the particle size and the
load of CNF required to reach a target paper strength. The analysis is based on a techno-
economic assessment using experimental data presented by Johnson et al. (2016) that is
shown in Table 4. In that work, the authors determined the load required to reach a target
tensile value of 10% above that of a hardwood base sheet by using CNF having different
fines content. As a practical approach, the fines content was correlated with the particle
size using SEM, e.g., a CNF slurry at 90% fines has dimensions at the nanoscale.
Measurements of the particle size for each fines content are not provided in the study.
However, it is inferred that for a low fines content, a material with a width at the microscale
predominates and the width moves towards the nanoscale as the fines content increases.
The energy required to reach each specific fines content was used as an input in the
manufacturing cost model for CNF proposed by De Assis et al. (2017). This model is based
on process data from a CNF pilot facility at the University of Maine, the same facility
where the experimental data used for this analysis were collected. Therefore, the
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manufacturing cost associated with each fines content was estimated, considering one ton
of dry CNF as the basis. The results are presented in Table 4.
Table 4. CNF Load Required to Increase the Tensile Value 10% Above of a Hardwood Base Sheet
Fines in CNF (%)
CNF Load (%)
Tensile index1 (N.m/g)
Manufacturing Cost2 (USD/t CNF Dry)
Hardwood base sheet 54.0 -
50 6.1 59.4 1,326
65 5.0 59.8 1,366
75 3.3 59.4 1,394
85 2.7 59.4 1,425
95 3.1 59.4 1,493
Note: 1Tensile index values from Johnson et al. (2016); 2Cost calculated using manufacturing cost model for CNF proposed by De Assis et al. (2017)
Figure 10 shows the CNF load cost per ton of finished product depending on the
fines content in the CNF used.
Fig. 10. Load cost required to achieve a 10% increase in the tensile index of a hardwood base sheet by using softwood CNF with different fines content. As the fines content increases, the CNF load decreases and levels off after a 75% fines content is reached.
As the fines content increases, the CNF load required to increase the tensile index
10% decreases and there is no significant difference in the required load after 75% fines
content is reached. These lower concentrations used in conjunction with the more
fibrillated CNF (fines content > 75%), offsets the high manufacturing cost. For instance,
when going from 50% to 75% fines, the CNF load cost is reduced by approximately 43%.
Based on the techno-economic assessment performed, it is possible to state that moving
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towards the nanoscale is economically justifiable, although, the question arises as to how
far one should go.
Starting from 75% fines content, the change of the load cost is less sensitive to the
fines content. This is because energy consumption tends to level off as the fines content
increases. A drop of 3% in the 95% fines CNF load (from 3.10% down to 3.01%), which
would be considered as a favorable scenario, would decrease the load cost approximately
2.3% with respect to the 75% fines CNF load (from USD 46.3 to USD 44.9 per ton of
finished product). This small change might make the producer skeptical about whether it
is worthwhile to pursue high levels of fibrillation. Therefore, other variables than just the
cost component must be considered in the decision-making process. As discussed
elsewhere in this review, there are challenges related to retention, slow dewatering, and
drying that need to be to overcome when using CNF as a paper additive which are more
likely to justify the use of CNF at a lower fines content.
OTHER ALTERNATIVES FOR FIBER REDUCTION
Dry Strength Additives Dry strength additives are commonly used in the paper industry as a way to
maintain strength properties with less refining or with lower quality fibers (Hubbe 2007a).
Figure 11 shows how dry strength additives can be used to reduce the amount of fiber
required to produce a specific strength target.
Fig. 11. The use of 1.2% cationic potato starch and 0.4% carboxymethyl cellulose produced a 42 g/m2 sheet with the same tensile strength as a 60 g/m2 sheet with no additives (adapted from Retulainen and Nieminen 1996)
A general characteristic of dry-strength additives, such as cationic starch, is that
strength gains may be cost-effective only up to a modest improvement in properties.
Limitations in achievable strength gains are often related to maximum amounts of the
polymers that can be absorbed by the fiber surfaces. Many of the paper machine systems
that might be considered as candidates for MNFC addition will already be using various
dry strength chemical additives at optimized levels, together with optimized levels of
refining of the fibers.
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A characteristic of using dry strength additives is that the sheet thickness is often
reduced compared to the case where no dry strength additives are present; in principle, this
might negatively impact properties such as bending stiffness and bulk (Retulainen and
Nieminen 1996). The latter are important components of packaging and tissue grades,
respectively. However, if the additive makes it possible to maintain strength at a lower
degree of refining, then the bulky nature of less-refined fibers might yield the opposite
overall effect. Because dry strength additives, with particular reference to cationic starch
and various acrylamide-based strength additives, are likely to remain used in applications
where strength might allow basis weight reductions, it is very important that future research
work includes evaluations of systems involving various combinations of MNFC and dry-
strength chemicals, working together.
Fines-enriched Pulp Fines-enriched pulp is produced using a high intensity, multiple pass refining
operation in conjunction with a fractionation process. In laboratory experiments, fines-
enriched pulp has been shown to be twice as effective as glue pulp (highly refined kraft
pulp used as a plybond enhancer) in terms of increasing multi-ply board strength, but it
negatively impacts sheet bulk (Björk et al. 2017). The properties imparted on the sheet by
the fines is heavily dependent on the fiber raw material (Fischer et al. 2017). Typically, in
a furnish with a high fines content, the fines have been generated by excessively refining
the fiber furnish, which breaks off more portions of the fiber layers, and even by fiber
cutting in extreme cases. Because the fines Björk et al. (2017) used to enrich the pulp were
generated during a separate refining process, this removes the negative impacts on paper
properties associated with fiber cutting in the furnish. Despite the negative effects of having
too many fines in the sheet, some fines must be present in the sheet to help with fiber-fiber
bonding and ultimately the strength of the sheet. Fines-enriched pulp could be an
alternative to MNFC; however, fines-enriched pulp produces a weaker, more porous,
rougher sheet of paper than in the case of adding MNFC to the furnish (Fischer et al. 2017),
which may not be desirable for some applications.
CONCLUDING REMARKS
Based on the literature reviewed, the authors have acknowledged the potential to
create value in the paper industry by introducing MNFC as a driver for cost reduction,
along with the potential challenges associated with said strategy. The high manufacturing
costs associated with the increase in fiber prices represent an opportunity for cost savings
through the reduction of fiber content in paper products. Standards for paper strength are
already established, and customers are not willing to pay a premium to have a super strong
product. Therefore, instead of using MNFC as a paper strength additive, the real business
opportunity may involve the use of MNFC to reduce the fiber content while delivering the
strength commercially required.
The fiber price for the furnish preparation is what determines the optimum amount
of MNFC to be used to maximize the cost reduction. For the techno-economic assessment
conducted in this review, the tensile strength was the only property considered as a
reference. Further research to evaluate the role of MNFC as a driver for fiber reduction in
low grammage papers, e.g., tissue and towel, and the impact that this reduction might have
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on other physical properties, e.g., water absorbency, bulk, and softness, needs to be
performed.
Likewise, the use of polyelectrolytes in combination with the MNFC represents an
alternative to further increase the cost reduction. For instance, an increase in MNFC
retention due to the use of polyelectrolytes could allow a reduction in the load required to
achieve a target tensile strength at a given grammage. At the same time, the development
of potential polyelectrolyte/MNFC synergies could also be beneficial in the task of
reducing fiber.
The use of MNFC as a paper strength additive also requires a feasible combination
of the particle size and load in the paper furnish. It was found that lower concentrations of
softwood CNF associated with high fines content (high degree of fibrillation) outweigh the
higher manufacturing costs. From an economic point of view, this justifies using
nanofibrillated cellulose instead of microfibrillated cellulose; however, operational
challenges related to retention, slow dewatering, and drying of the nanocellulose might also
need to be considered to select one type or another.
Finally, another important aspect to bring into the discussion is the fiber source
used for the MNFC production. Thus far, energy processing cost had been noted as an issue
in the manufacturing of MNFC; however, a recent study showed that the fiber source is the
major cost driver. The cost of the cellulosic fiber typically represents more than 60% of the
total manufacturing cost (De Assis et al. 2017). Johnson et al. (2016) stated that for high
fines content (> 95%) both hardwood and softwood CNF show an equivalent performance
when added into a paper furnish. Therefore, the most profitable alternative would consist
in using the MNFC manufactured with the pulp fiber with the lower price; however, this
might not be true for MNFC with an intermediate fines content. The latter highlights the
need to conduct research considering several fiber sources and fines contents in
combination with different polyelectrolytes. The authors believe that, on top of the gain in
the paper strength, the key point to select the nanoscale and the specific fiber source used
for the MNFC production will depend on additional improvements in other physical
properties powered by the nano-feature that could potentially add extra value to the paper
grade produced.
REFERENCES CITED
Abdul Khalil, H. P. S., Bhat, A. H., and Ireana Yusra, A. F. (2012). “Green composites
from sustainable cellulose nanofibrils: A review,” Carbohydrate Polymers 87(2),
963-979. DOI: 10.1016/j.carbpol.2011.08.078
Abdul Khalil, H. P. S., Davoudpour, Y., Islam, M. N., Mustapha, A., Sudesh, K.,
Dungani, R., and Jawaid, M. (2014). “Production and modification of nanofibrillated
cellulose using various mechanical processes: A review,” Carbohydrate Polymers
99, 649-665. DOI: 10.1016/j.carbpol.2013.08.069
Afra, E., Yousefi, H., Hadilam, M. M., and Nishino, T. (2013). “Comparative effect of
mechanical beating and nanofibrillation of cellulose on paper properties made from
bagasse and softwood pulps,” Carbohydrate Polymers 97(2), 725-730. DOI:
10.1016/j.carbpol.2013.05.032
Ahola, S., Österberg, M., and Laine, J. (2008). “Cellulose nanofibrils - Adsorption with
poly(amideamine) epichlorohydrin studied by QCM-D and application as a paper